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    Photophysical and catalytic properties of multicomponent metal-organic frameworks : a thesis presented in partial fulfilment of the requirements for the degree of Doctor of Philosophy in Chemistry at Massey University, Manawatū, New Zealand
    (Massey University, 2021) Cornelio, Joel
    Multicomponent metal-organic frameworks (MC-MOFs) are crystalline, porous materials built from multiple geometrically distinct organic ligands. The ligands are located in specific lattice sites in the MOF. The properties of these materials can be tuned by incorporating ligands with functional groups for a desired application. This thesis deals with studying the applications of MC-MOFs named Massey University Frameworks (MUFs) for luminescence, energy transfer, photochromism, and catalysis. Firstly, we obtain white-light emission in MC-MOFs from the combination of blue and yellow luminescence of the ligands. The trends observed in the emission spectra originate from inter-ligand energy transfer interactions. These interactions have been explored further using a variety of crystallographic and spectroscopic techniques including time-resolved luminescence at the nanosecond and picosecond timescales. In another chapter, we have studied photochromism in some MC-MOFs which is caused by light-generated organic radicals. The differences between their radical and non-radical forms has been elucidated using X-ray crystallography. We also research the impact of pore environment on the outcome of an enantioselective intramolecular aldol reaction catalysed by MC-MOFs. Finally, a number of ideas are proposed as part of future work, that take advantage of the multicomponent nature of these materials.
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    Synthesis of multicomponent metal-organic frameworks and investigations of their physical properties : a thesis presented in partial fulfilment of the requirements of the degree of Doctor of Philosophy in Chemistry at Massey University, Manawatu, New Zealand
    (Massey University, 2019) Alkaş, Adil
    Multicomponent metal-organic frameworks (MOFs) are built up from multiple ligands that are geometrically distinct. These ligands occupy specific positions in the MOF lattice. Installing different functionalities at precise locations in the framework is an important step in making MOFs for specific applications. This can be achieved by designing functionalized ligands for multicomponent MOFs. This study was, firstly, focused on design and synthesis of new linkers. The study then covered preparation of a number of quaternary MOFs. Furthermore, the study was focused on the physical and chemical properties of these MOFs, such as their catalytic activity, gas adsorption and fluorescence behaviours.
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    Interior decoration of metal-organic frameworks through a thermolabile protecting group strategy : a thesis presented in partial fulfilment of the requirements of the degree of Doctor of Philosophy in Chemistry at Massey University, Manawatū, New Zealand
    (Massey University, 2019) Jameson, Heather
    Metal-organic frameworks are porous nanomaterials of modular construction that have shown themselves amenable to different modes of functionalization. Thermolytic deprotection (thermolysis) of incorporated thermolabile protecting groups (TPGs) has been one of these methods applied to tune the chemistry of MOFs and their material properties, accessing otherwise unattainable MOF topologies with enhanced porosity and reactive functionalities of particular interest in gas storage and separation and catalytic applications. In this thesis the TPG post-synthetic modification (PSM) technique is expanded upon in two ways. Firstly, through investigation of mono-and dual-functionalization within a flexible pillar-layer MOF family: localization of the TPG, influence on framework topology and gas sorption characteristics. Secondly, in synthesis of a set of novel ketene-protecting TPG ligands: ligand characterization, and endeavours at MOF incorporation.
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    Thermolabile protecting groups in metal-organic frameworks : a thesis presented in partial fulfilment of the requirements of the degree of Doctor of Philosophy in Chemistry at Massey University, Manawatu, New Zealand
    (Massey University, 2016) Blackwood, Sebastian
    Prior to the work carried out for this thesis, there were no publications in which bpy was used as a ligand backbone, or in which a carboxylate was incorporated into a MOF using a TPG. Also, to the best of our knowledge there are no examples in the literature of an ethyl carbamate TPG in MOFs. In this thesis the range of TPG protected ligands has been expanded to include 1,4-bdc (Chapter 2) and bpy (Chapters 4 and 5). The bpy-NHBoc and bpy-TBE materials are the first examples of N-donor type ligands protected by TPGs. Furthermore, the bpy-TBE ligand is the first example of a TPG protected carboxylate in a MOF. In Chapter 2, 1,4-bdc-NH2 was protected as both the ethyl carbamate and the tert-butylcarbamate, giving 1,4-bdc-NHCOOEt and 1,4-bdc-NHBoc, which there then incorporated into a MOF-5-type framework. It was envisaged that thermolysis of the carbamate esters could generate an isocyanate group, though this was not expected for 1,4-bdc-NHBoc due to the tendency of tert-butylcarbamates to decompose to the amine. Despite thermolysis on the TGA apparatus only generating the amine, it was found that thermolysis under vacuum enabled not only enabled ~ 60 % conversion of the ethylcarbamate to 1,4-bdc-NCO, but also a ~20 % conversion of the tert-butylcarbamate to 1,4-bdc-NCO. The MOF-5 analogues in this work also proved sufficiently stable to survive the thermolysis conditions with little discernible effect on the porosity of the material. In Chapter 3, 1,3-bdc-NH2 was protected as both the ethyl carbamate and the tert-butylcarbamate, giving 1,3-bdc-NHCOOEt and 1,3-bdc-NHBoc, which there then incorporated into a lon-e-type framework. It became apparent the lon-e was a poor choice in MOF for use with TPGs as the framework was prone to collapse from desolvation, and it was not possible to thermolyse the materials without complete collapse of the MOFs. In Chapter 4, bpy-NH2 and bpy-CO2H were protected with TPGs to give bpy-NHBoc and bpy-TBE respectively. The ligands were combined with bpdc and zinc to obtain the BMOF-1-bpdc analogues MUF20-Aβ and MUF20-Aγ. Whilst the thermolysed materials MUF20-Aβt and MUF20-Aγt demonstrated significant gas uptakes compared to their protected counterparts, comparison of MUF20-Aβt with the directly synthesised material MUF20-Aβ’ revealed significantly higher uptakes than the thermolysed materials. This discrepancy indicates that the BMOF-1-bpdc/MUF20 framework is partially degraded under thermolysis conditions. These results strongly imply that this framework is not compatible with TPGs. However, TPGs did allow for the installation of a carboxylate group into the BMOF-1-bpdc/MUF20 framework which was not obtainable through direct synthesis methods. In Chapter 5, bpy-TBE was combined with btb and Zn/Cu to obtain Zn-DUT-23-TBE and Cu-DUT-23-TBE. These materials were then thermolysed to produce Zn/Cu-DUT-23-CO2H, materials that were not able to be directly synthesised using bpy-CO2H. Unfortunately, the thermolysed materials demonstrated significant decreases in uptakes compared to their protected counterparts. However, the TPG containing materials also had markedly lower uptakes than the parent Zn-DUT-23 and Cu-DUT-23 materials, which has been attributed to pore collapse. This partial pore collapse may have sufficiently weakened the MOF framework to increase its sensitivity to the thermolysis conditions, resulting in a much larger decrease in uptake than would have been the case with a defect free material. The results of this thesis revealed that MOF stability is a key factor in the compatibility of a material. Specifically, the MOF must be resistant to solvent removal and subsequent heating at elevated temperatures for extended periods. This is most clearly observed in Chapter 3, where the lon-e materials were very susceptible to solvent removal, and later were completely collapsed by thermolysis. These findings have led to the recommendations outlined in section 6.2 for the screening of MOFs for their compatibility with TPGs.
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    Multicomponent metal-organic frameworks : a thesis presented in partial fulfilment of the requirements of the degree of Doctor of Philosophy in Chemistry at Massey University, Manawatu, New Zealand
    (Massey University, 2015) Liu, Lujia
    Introducing multiple functional groups into the pores of metal-organic frameworks (MOFs) promise sophisticated properties. Precise control over the position of these functional groups would enable the 3D chemical environment of discrete void spaces to be tailored. This was an outstanding challenge prior to this work. In this thesis we present a study of the synthesis, characterization and properties of MOFs that can meet this goal. These MOFs are multicomponent in nature, being built up from three geometrically distinct organic ligands. Functional groups can be appended to these ligands and are incorporated in precise locations and with perfect order in the frameworks. The chemical environment of the pores of these MOFs is “programmed” by these functional groups. MOFs constructed in this way give rise to exceptional gas adsorption characteristics, unexpected stability towards water vapour, and tunable catalytic properties.